Azo dye intermediates of the anthraquinone series



Patented July 10, 1951 UNITED STATES AZO DYE IN TERMEDIATES OF THE AN THRAQUIN ON E SERIES No Drawing. Application June 17, 1949, Serial No. 99,871

6 Claims. (Cl. 260207.1)

This invention relates to the preparation of new dye intermediates of the anthraquinone series which are more particularlyazobiphenylcarbonylaminoanthraquinone compounds.

While a number of vat dyes in the yellow range have been used in the dyeing and printing of textiles, the fastness properties of these yellow colors are poor as compared with the fastness properties of many of the other colors in the vat dye class. Where yellow dyes in this class with improved fastness properties have been found, they in turn are either dull or weak tinctoriaily and therefore the various yellow dyes in the vat dye class are chosen to answer a particular need, balancing the question of fastness, brightness and cost of the particular dye available.

It is an object of the present invention to produce new and valuable dye intermediates particularly useful as acylating agents in the manufacture of yellow vat dyes of desirable shades, which dyes exhibit improved tinctorial strength and fastness properties over previously known dyes of similar shade. It is a further object of the invention to produce new dye intermediates which themselves can be ring closed to form vat dyes having good tinctorial strength and fastness properties.

The compounds of this invention have the following general formula:

pared by reacting an ortho-halogen-substituted beta-aminoanthraquinone with 4,4-azobiphenyl- 4,4-dicarbonyl chloride in substantially equal molecular quantites in an inert solvent under anhydrous conditions. The reaction is preferably carried out at temperatures of from 1209-200 0., and the resulting products are isolated by filtration and recovered in substantially quantitative yields. In this reaction the condensation of the beta-aminoanthraquinone appears to take place substantially quantitatively on one end of the dicarbonyl chloride only, for by analysis the resulting product appears to be uniform in its composition and substantially a pure compound. This is also borne out by the fact that, on subsequent reaction to produce other and valuable I dyes, it reacts as a substantially pure compound. The halogen beta aminoanthraquinone employed is preferably the l-halogen-Z-aminoanthraquinone or the 1,3-dihalogen-2-aminoanthraquinone, although the compounds resulting from the 3-halogen-Z-aminoanthraquinone are also obtained in a good yield and serve as valuable intermediates in the preparation of other vat dyes of excellent dyeing and fastness properties.

When the compounds of this invention having the formula above given are further reacted with aminoanthraquinones or aminothiophanthraquinones followed by ring closures such as may be eifected in the presence of soda ash, potassium acetate, and condensation catalysts as more particularly described in copending applications Serial No. 99,873 and Serial No. 99,877 1,2(N)- oxazoles, which are yellow dyes of extraordinary tinctorial strength and fastness properties, are obtained in excellent yields. I

The following examples are given to illustrate the invention. The parts used are by weight.

Example 1 zene; 0.5 part of pyridine and 77 parts of 4,4-

azobiphenyl 4",4' dicarbonyl chloride are Thirty (30) parts of l-chloro-2-amlnoanthraadded while agitating and the mass heated to quinone are suspended in 800 parts of nitroben- 138-1 l0 C. and maintained for 6 hours. It is Zane; 03 t of pyridine and 54 parts of cooled to 125 C. and treated with ammonia for 4 ,LuazobilahemdA yndmarbonm chloride are 3 to 4 hours. After cooling the mass is filtered,

washed ith benzene, alcohol and hot water in added while agitating, and the mass heated to tum f dried The product forms a Weak 1330-142 and maintained for 6 hours- It is yellow powder. It is obtained in good yields and then cooled, filtered, washed with benzene and in has the following probable formula:

dried. The product forms a pale yellow powder On conversion to the oxazole as described analyzing 10.20% chlorine (calculated 10.44%) above, it afiords a greenish-yellow vat dyestuff and is obtained in a yield of 98% of theory. It is of good tinctorial strength and fastness, particconsidered as having the following formula: ularly to light.

0 o1 I I Example 2 Example 5 Fifty parts of 2-amino-3-bromoanthra- A mixture of Z-amino-l-bromo-twhloroanquinone are suspended in 1250 parts of nitrobenthraquinone (3.35 parts), 4,4-a-zobiphenylzene; 0.5 part of pyridine and "16 parts of 4, l'-azo- 4",4"-dicarbonyl chloride (4.6 parts) and dry biphenyl-4",4"-dicarbonyl chloride are added nitrobenzene (80 parts) was heated 6 hours at While agitating and the mass is heated to 140 35 14'0-l50 C., cooled to 80C., filtered and washed C. and maintained for 2 hours, then heated to with dry nitrobenzene and benzene. A good yield 208-2i0 C. and held for hour. It is then of the bright yellow mono-acid chloride is obcooled, filtered, washed with benzene and dried. tained having a melting range of 355-357 C. The product forms a pale yellow powder and is with decomposition. It has the formula.

obtained in excellent yield. It is represented by Example 6 the formula: Sixty parts of 4,4-azobiphenyl-4,4"-

ple 3 dicarboxylic acid (sodium salt) are suspended 1111200 harts oi lii i parts of pyri- Twentsw-five (25) parts of l,3 -dibromo-3:anihiehyl chloride a added inoanthraquinone are suspended dine and 50 parts of 't 1n 5 EIZI'ODBILZBIIE; 0.3 part of pyridine and 3 0 111?; Si While agitating and the fi 1s ffiiie? a i, -azo i hen d for 12 ours. g

D V1 4 ,4 d1carbon 1 hl are C. and maintalne (to take out excess of $5 g ne a d the mass heated to blown for o -hal ,n f.

an main a 7 heated to 195, ,C. n ii elfi io i gger r 1 t: 5 1 115t5- oanthr eu nen are as then cooled, filtered, washed with benzene and added. Them-Si is heate to135+138 o gd a l' The resulting dibromo compou d forms maintained for 6 hours. It is cooled to 60 eo $15132 powder and is obtained in very 25 parts of methyl alcohol are added and the mass is heated to -135 C. and maintained Y for 3 hours. After cooling, the mass is filtered, F y (40) parts of 1-chloro-2-aminoanthrathe cake washedwith nitrobenzeneand then with qulnone are suspended in 1500 parts of nitroben- 75 alcohol, and dried. The product forms a weak Example 4 "d cool d to 50 0., then 33.

, yellow powder. It is obtained in good yields, and the usual alkaline hydrosulfite vat, and shows has the following formula: scarcely any solubility in caustic alkali solution.

The product is pale yellow, gives a brownish On acidification of a brown alkaline suspension vat, but has little affinity until converted to an I of the free acid compound it turns from brown oxazole. to yellow, indicating the formation of the free v Example 7 acid compound. By replacing the methyl alcohol in Example 6 With the exception of those containing the with 50 parts of dodecyl alcohol,'a product havfree acid chloride group the compounds of this ing the following formula is obtained: invention, including the long chain alkyl esters,

(I) Cl It is a pale yellow solid, much more soluble in may be readily converted to vat dyes by effecting: nitrobenzene than the methyl homolog, which is ring closure of the oxazole group. This mayb sparingly Soluble even at e ated te p carried out in nitrobenzene or other solvent by In the same manner as illustrated in the above means of a copper condensationcatalyst and in. examples, any of the aliphatic alcohols conthe presence of an acid binding agent. If demining m 1 0 1 carbo ato s m y be e sired, the ring closure may be eifected in the ployed instead of the methyl alcohol or the (10- same solvent and without isolation from the redecyl alcohol to give compounds carrying the action mass in which it was formed by the conester group which are valuable dye intermedensation of the dicarboxylic acid chloride and diates. These esters may be readily hydrolyzed n the halogen aminoanthraquinone. to the free alcohol by heating in aqueous causic 05 The 4,4-azobiphenyl-dicarboxylic acid emsolution or in alcoholic caustic solution. ployed in the above examples is readily prepared Any of the compounds of this invention conby the sodium hydroxide-glucose reduction of. taining the free acid chloride group such as il- 4,4-nitrophenyl benzoic acid. 'The dicarboxylic lustrated in the above examples may be readily acid is converted to the acid chloride by treating converted to the compounds containing the free 40 the .free acid or its sodium salt with thionyl chlocarboxylic acid group, by dissolving the acid ride, or phosphorus pentachloride in an inert sol chloride compound in concentrated sulfuric acid vent such as aromatic hydrocarbons or the chloat from 5 to 10 C. This effects the hydroysis rinated or nitrated aromatic hydrocarbons. The of the acid chloride group, with the liberation of 4,4'-azobiphenyl4",4"-dicarbonyl chloride has hydrochloric acid. These compounds containing a melting point of 260-262 C.

the free carboxylic acid group are yellow-brown We claim: powders which vat readily to an orange-brown 1. The compounds of the general formula:

0 solution. (The acid chloride compound before hyin which at least one X stands for a halogen of drolysis is not readily vattable.) The compound the group consisting of chlorine and bromine containing the free carboxylic acid group disand R is a substituent of the group consisting of solves in sulfuric acid with an orange-brown color -0I-I, -NI-I2, -Cl and Oalkyl, which alkyl and without further evolution of hydrochloric 0 group may contain from 1 to 18 carbon atoms. acid. It has very little affinity for cotton from 2. The compound of the formula:

3. The compound of the formula:

4. The compound of the formula:

5. The compound of the formula:

6. The compound. of the formula:

0 Cl ll 1 JOSEPH DEINET.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS Number Country Date 348,018 France July 17, 1939 HERMAN E. SCI-IROEDER. 

1. THE COMPOUNDS OF THE GENERAL FORMULA: 